Water purification



NOV. 20, E* J. RYAN WATER PURIFICATION 2 Sheets-Shes*v l Filed March 6, 1950 tmuxxo Nov. 20, 1956 E. J. RYAN WATER PURIFICATION 2 Sheets-Sheet Filed March 6, 1950 n my wn/z www laf/@Wfl r e e rt m M w LAI- Flin im lw\\\v\\\\\\\\ v.\c`. .n ../.fo 2m @.XAQNUWMDHTQ @1MM BY United States This invention relates to purification of water with a gaseous activated oxidizing agent and further to the impregnation of water with substantial quantities of gaseous oxidizing agent wherein the water may serve as a carrier therefor for application of such gaseous oxidizing substance for various oxidizing purposes such as bleaching or purification of other materials by oxidation.

The gaseous oxidizing agent hereof is a new type and is described and claimed in my copending application Serial No. 142,831, filed February 7, 1950, now Patent No. 2,637,688, issued May 7, 1953, of which the present application is a continuation in part, that patent being a continuation-impart of application Ser. No. 50,199 now abandoned.

According to one phase of the present invention, water in various stages of purity and containing various organic contaminants, is treated with an activated oxidizing gas to purify the same to lrapidly completely or partially, destroy the organic matter. By the term purification, as used herein, it is intended to include destruction of bacteria and at least partial destruction of any oxidizable organic matter that may be present. The activated gas hereof, while destroying the bacteria apparently oxidizes some of the finely suspended or dissolved organic matter and thereby removes color, where such organic matter imparts a color to the water, as well as odor, where the organic matter and/or bacteria imparts an odor to the water, and leaves a bacteria-free clear colorless and odorless water.

Waters in various degrees of contamination may be purified according to the present method to convert the same to bacteriaand organic-material-free water generally of crystal clarity which is substantially tasteless and odorless in the concentrations of gas used. Thus, this water purification is usefully applied to contaminated large bodies of water such as rivers, bathing and beach water, drinking water, drinking water systems containing drinking water and Water used for machinery cooling and plant processing, as well as sewage or Waste waters containing suspended organic matters generally dispersed into running streams and tending to contaminate the same. Thus, waste waters of rivers, harbors, flowing streams, stagnant ponds, as well as waste water liowing through pipe lines for disposal or to be used in factory processing of various materials particularly organic may be treated for purification according to the present process.

Another important application in the purification of water is the purification of field waters from local wells and streams which of necessity, must be used either for making up uid drilling muds at the site of a well drilling or in the use for waters for ushing oil where oil flush` ing methods are used in the extraction of oil from a well, or in merely cleaning the well. The problem of preventing bacterial contamination which results from rapid atent in the clogging of the vsand interstices as well as the oil lines from the well byt'arry, waxy and slimelike deposits of organic matterresulting from such bacterial action upon the oil, has been acute. According to the present method the available vicinity waters of any degree of purity may be treatedto purify the same. Where relatively crude local waters are to be used in very large quantities the oxygen polymerized in the presence of halogen with or without further contact with halogen containing catalyst may be used.

Similarly it is a useful application of the present invention to decontaminate sea water, normally pumped through ship lines into fuel oil tanks for ballasting of tanks and displacement of the oil as it is used. The inhibition of bacteria growth in these waters results in clean systems, free of organic residue formed by bacterial decomposition of the oils.

The preferred water purifying gas used herein is an activated polymeric form of oxygen whose preparation is described in greater detail in my co-pending applications above referred to. Reviewing the process of forming the gaseous water purifying agent, warm substantially pure oxygen is first subjected under pressure to radiant energy such as ultra-violet light having a wave length of 2,000 to 4,800 angstrom units. Thereafter, the gas is treated by high voltage discharge of the order of at least 5,000 volts and preferably higher, such as 11,000 to 18,000 volts, but higher voltages as described therein may be used. During these treatments the oxygen gas is maintained under a substantial pressure of at t least 10 pounds gauge; higher pressures generally tending to a greater degree of polymerization. Generally a pressure in the range of l0 to 50 pounds gauge will be used but higher pressures in the range of 100 to 10,000 atmospheres may be used for very large installations t where rugged constructions of apparatus to withstand growth in the presence of oil and which generally results Y 1 such pressures are economical. The oxygen gas is also preferably heated to a temperature generally exceeding F., operation in the temperature range of 100 to 200 F. being generally satisfactory; however, higher temperatures up to 600 F. will operate.

The oxygen gas so treated is substantially entirely in polymerized form and may be used as such but preferably is generally thereafter modified by halogen containing catalyst, or according to a modification hereof, the oxygen may be modified in the presence of halogen with or without subsequent treatment with a halogen containing catalyst.

The halogen containing catalyst consists of a concentrated solution in water of halogen either as pure elemental halogen dissolved in water, or a water soluble inorganic halogen salt dissolved in water. The halogen may be either elemental halogen (chlorine, fluorine, bromine, or iodine) or soluble inorganic salts thereof, such as sodium, potassium, lithium, magnesium, barium, strontium or calcium, halides, halates, halites, hypohalites, or oxy-halides. Specific examples of an inorganic halogen salt or element are sodium chloride, sodiumV bromide, sodium fluoride, sodium iodide, free elemental iodine, free elemental chlorine, free elemental bromine, free elemental fluorine, sodium hypo-iodite, sodium hypofluorite, potassium trio-iodide, potassium hypo-chlorite, potassium bromate, sodium tri-iodide, potassium hypochlorite, potassium bromate, sodium acid fluoride, `sodium periodate, sodium hypo-chlorite, sodium acid uoride, lithium periodate, sodium hypo-chlorite, chlorine di-oxide, calcium iodide, barium chloride, strontium chlorate, magnesium chloride. Mixtures of such halogen Imaterials in many instances are desirably used. The elemental halogen or salt thereof is generally used asl a concentrated solution in water. In normal operation the 3 aqeous Solution is saturate! Withrsspsst t9 the tre@ halog'enmor'salt"tliereofmand," to maintain the saturation, an excess of salt or elemental halogen is usually present as a slurry r suspensie?, in, the water, but this not ,aecssaty'siri ahy'cocefit'rated @elution Qf halos@ @r salt th' f'iv'weter' will anstatt and, the sementi-ation of halogen material. may vary anywhere fram. 2.5% up. te niblte 'Saturation este@ Upea the quantity Qt the partiiularf halogen material which will dissolve.

v"Other substantially. inert salts may be used in the catalyst solutionprirnarily to raise the gravity of the halogen containingliqulid td give optimum Washing contact with the oxygen'polymer passed therethrough and also to. sive improyed Solubility'eiests. @t the halogen,- Such inert salts 'as' the lsoluble sulphatesr. areI suitable and the l-iquid'ill Which the *halogenr is dissolved may be such as alr'ead'yfhave a natural halt'agen` content as well as lesser quantities of other salts, for example, natural halogencontaining brines including ordinary sea water'. It will be understood that sea water whenI used will generally be further fortified with the halogen to substantial satmanen'.

Ifdtmng the halogen activated polymeric oxygen sas, the pure oxygen, polymerizedA b ysubjection to4 r'adiant'ener'gy andr'highvoltagedischarge, is bubbled through the saturated aqueous halogeny containing catalyst inthe'pressure yand temperaturerange givenabove and at a ratevariable withlthe size of they apparatus. For example, for forming small quantities a2 useful rate is about 1/2` to, le() liters'of gas per liter of aqueous catalyst per lminute.

The gas obtained is then, used inthe water purification herein described. Such gas may be used directly as produced or maybe compressed and/ or liquified, stored andre-evaporatedfor subsequent use, However, it ispreferred to use ythe gasy directly as obtained'from the catalytic treatment.

The gas obtained'prior tocatalytic treatment `is valready substantially polymeric. Iu do not know the, complete analysis of this gas. v The polymerized gas probably contains a substantial-quantity ofozone, but it isbelieved further to contain substantial quantities of higher polymer'sof oxygen. Thus thefgas by the particular ozonizingrphysical'treatments hereof startingwith pure oxygen gas contains ozone, residual quantities ofpure'oxygen andisubstantial'quantities of other forms of. oxygen unanalyzable. After passing throughv the halogen',cata lyst the gas is highly activated and'it appears probable thatthe halogen of lthe salt :in the catalyst ysolutio`n itself isoxidized tofree-halogen and some of which is vaporized v andentrainedfbythe polymerized-oxygeny gas. However, the activity of the gas appears to in'dicatethat the polymer. containing oxygen is fui-ther polymerized yin the catalytic,contactoiincrease the Aquantity of `higher polymerio oxygentherein.. It: is also possible lthat the halogenitself.vaporizedinto the polymerized oxygen gas stream is alsooxidizedandmay be present in the form offahalogenoxide, Whatever the case is, I am not certain, and thereforey donOtntendto be limited by any theoryasto the exact. chemical-reactions which do take piace in theseveral. reaction stages. It appears at presentrnost probablethat the gas in additionl to lpolymeric oxygen. lwith; `some Acontent of. higher-polymers `of oxygen as well as sozone,. further contains some halogen whichy maybe dfree ..oroxidizedV I therefore use the termV halogen activated polymeric oxygenr to define thegas kherein obtained by halogentreatment in--the gaseous or liquid catalyststate..

The oxygen gas after. .ultra v.violet light treatment and methoddescribed herein for producing polymericoxygenprior to passing thevsame through/the halogencatalyst.

. However, it is possible to further activate ordinary ozone formed from oxygen by passing such ozone through the halogen catalyst, but such gas is not so highly polymerized and less active.

Thus, within the scope of the present invention, applicant first produces a polymeric oxygen gas preferably by subjecting the oxygen gas under heat and pressure rst to ultra violet light and then to high voltage discharge to form a gas so highly polymerized as to be direct-ly useful in water purification, but other sources of polymeric oxygen such as an ordinary' ozone generator may be substituted as the sourcefofthe polymeric oxygen. The polymeric oxygen obtained by the preferred polymerizing procedure is preferably passed through the halogen containing catalyst and is then ready for introduction into water for purification thereof according to the present invention. Where ordinary ozone is used as al source of polymeric gas, the treatment with halogen isI essential, but even. halogen treatment of ozone does not give aV gas ofi equivalent; activity to that polymerized by the preferred method.

I n a, modication, of` the. present invention it is also possible to introducepure halogen. preferably gaseous' into the, oxygen( priorV to polymerization thereof so' that the polymeric oxygen after subjecting to ultra violet light-` and. high voltage discharge, contains from 1 to 25%, preferably 5to7 1,5%` of halogenk either as freelialogenl or halogenin an` oxidizedand possibly polymerized form or combination thereof'. The polymeric oxygen, gas con.-

tainingv halogen is preferably then; passed through thev halogen containingY catalyst and then` used-y in water puricatio'n. However, in this case where heavy rapid. dosages of gas is to be applied to crude waters such as swamps or large areas,` to be decontaminated, the mixture off polymeric oxygen and halogen may be directly applied withoutH further catalytic treatment.

`In treatment of,` water for drinking purposesrthewater, ifNv it' contains, inorganic and organic sediment,` may be rst' conventionally filtered" to remove such suspendedl matter but where commercial waters, waste water or large bodies ofwater are merely to be generallyI puried for purposes-other than drinking, ltration is optional: The-water is treatedwhere it'is'a stagnantbody suchas infa'tank, Iriver, bay or pond, etc. by bubbling the f' gas through' a substantial head 'of'water, i. e. lv to 15 foot heador more, Any quantity of'th'e gas soluble in water may be applied.` The gas to destroy the bacteria and oxidize organic matter must contact the water which is effected by aerationofthe Waterwith the gas for intimate contact thereof.v Bacteria as shown by the examples below-aresubstantially immediately destroyed upon contact withgthe gas: Hence, it is" not'essential for purposesof merely destroying bacteriagthat'any substantialiresidual quantity `offthey gas 'remain dissolved in the water, and any applicationv to Vgive a homogeneous aeration 1throughout the-water will'suiiice., Effective oxidation however, of substantial quantities -of organic matter requires sutilcient oxygen-supplyto'lreact therewith. The' adequacy of the: activated'lgas supply* for/such purposes maybe tested by analysis of the'bacteria content of'the'water after treatment'l or--theresidual 'dissolved gas content. Any` residual dissolved-content lof'such gas indicatingthat effective aeration' and oxidationhas takenplace; and anexcess -of gas has 'been applied. Larger excesses than aresidual dissolved-gas content `iof *3 0' pr p: m. would not generally be used, but such excess is not a critical factor, and largerquantities-'may'be applied Ato. any water, the quantity Iconsiderations'being largely'economic.

Whilefallfwthe halogen-s arecuseful in the 'purication'of contaminated 1waterstas described 'hereinrthe halogens are not-full `equivalents in -their effectfon' various' types 'of contaminants, and-^`willbe 'selectedgenerally on the basis 'ofi-'the type -of contaminant contained` inl thev water. Thus-yl alll halogens will' v'destroyjbrIcteria 'within a-1short period -of ltime-asr^shown-in nthe lexamplesebelow. It is found that the heavy halogens, bromine and preferably iodine are particularlyeffective where a spore forming bacteria, such as tetanus and/or parasites and/or fungi are encountered in the water, and it is desired not only to kill the same but also destroy the spores thereof where they occur. For this purpose the halogen iodine is most effective and the rapidity of destruction of spores, parasites, 'or fungi decreases with the lighter halogen, bromine and its salts being the next most effective.

Where the water is to be used for drinking purposes and particularly with a view to having a desirable fluorine content, for its known effect to inhibit dental caries, the fluorine type of halogen would be preferred. Thus, it would be used for drinking water purposes where the water is not highly contaminated with bacteria and its bacteria is generally not of the spore forming type. However it is usual for these effects to use a mixture of the dierent halogens to effect the several results.

I-t will be understood however, that all of the halogens have a utility in destroying bacteria varying with the time and concentration of contact, and for purpose of general economy and availability chlorine is generally used for most commercial and industrial applications and would be used in any case except in the specific instances where high contamination with spore forming bacteria is encountered, in which case iodine would be preferred; or uorine where it is desirable to impart a specific fiuorine content for purposes of improving the Water to inhibit dental caries in certain drinking waters, and generally mixtures thereof would be used.

In a preferred form of operation of the present invention the apparatus as described particular-ly in applicants copending application wherein the oxygen gas is directly polymerized and halogen treated, is immediately bubbled into a pipe line carrying the water.

It will be understood that to impart a requisite quantity of oxygen a certain volume of gas may be diffused into a pipe lin-e in proportion to the amount of water passing therethrough and at some subsequent stage, the excess gas, which is not dissolved, may be removed. In batch treatments the gas may be merely bubbled upwardly from the lbottom `of the tank or body f water having from l to l foot head or more over a period :of time such as from 5 to 30 minutes or longer, rsufficient to yox-idize -a desirable portion of the organicvmatter content therein and sometimes allow a residual content of dissolved gas.

The drawings herewith illustrate the apparatus for effecting the invention and for the application thereof.

Fig. 1 shows `a diagrammatic flow sheet or plan of use of the gas generator hook-up to an ordinary pump line system carrying the water of any quantity for purification thereof.

, Fig. 2 is a detailed view showing application of activated gas for aerating stagnant waters in a tank, pond, pool etc. :or even owing waters unconfined, in a stream.

Fig. 3 illustrates the application of activated gas to oil wel-l operations for purification of waters and drilling fiuids used therewith.

The apparatus set forth in the drawings herein shows diagrammatically a hook up for treatment of water being carried through a pipeline 10. The apparatus shows pump 11 which supplies water to any series of filters of conventional construction 12 and 13, hooked up through a pair of four-Way valves 14 and 15, to allow operation of the filters either singly `or in series whereby one of the filters may be cleaned while the other is in operation.

, The water is then passed through a diffuser chamber 16 which contains a diffusing member 17 situated so that the water will either pass therethrough lor in close proximity thereto. Such member 17 may be a series of perforated pipes, porous stone or porous meta-l through lwhich either gas or water 'or both may pass. The water containing gas bubbles is then passed through a gas separating chamber 18 which is merely a container large enough to slow the passage of water and alow the gas to separate as bubbles, the water being withdrawn through a pipe 19 and the separated gas overhead through a pipe 20. The evolved spent gas may be either wasted or recycled through a line 21 to the inlet of the gas activating apparatus for reactivation and re-use.

As indicated, details of the apparatus for activating the gas are set forth in applicants copending applications, the present drawing showing the same only in diagrammatic form of which a supply of gas 23 as recycled gas obtained with the aid of pump 22 from lines 21 as withdrawn from the gas separating chamber 18, is used, or an extraneous source of pure oxygen from a compressed oxygen tank 24 is used alternately through any threeway valve 25. The gas at a pressure of approximately 10 to 50 lbs. per square inch gauge, for example 40 lbs. per square inch gauge is passed into chamber 24 which contains heating elements and thence to a chamber 26 which contains a source of ultra-violet light to raise the temperature of the gas to the range of to 200 F., for example, F. and irradiate the same. The gas, after treatment by ultra-violet light in chamber 26 and under the pressure and the raised temperature is then passed into a chamber 27 wherein it is subjected to a high voltage discharge preferably in the range of 11,000 to 18,000 volts such as about 15,000 volts whereby the oxygen is converted to a polymeric form. The gas is then bubbled through the catalyst tank 28 containing an aqueous solution, preferably saturated, of halogen or halogen salt as described above, for example, a saturated solution of sodium chloride. The evolved gas then passes through line 29 into a diffuser plate or perforated pipe 17 for distribution to the water being treated. From time to time additional halogen salt may be added as a slurry from a hopper 30 to the catalyst tank 28 or pure halogen gas such as chlorine or fluorine may be supplied from a compressed halogen tank 31 which leads directly to the catalyst tank through line 32 or by way of a three-way valve 33 is mixed with the warm oxygen prior to polymerization. As a modification of this invention, as pointed out above the halogen may be mixed with the oxygen in tank 24 in proportions of about 1 to 25%, for example, 10% and thence passed through the polymerizing system therewith. Accordingly, in the system thus shown, the water is treated in a pipe-line by bubbling halogen activated polymerized oxygen gas therethrough and then undissolved gas from the separating chamber 18 is recycled to the system. Such is a highly economical method of treating the water wherein a substantial bulk of the gas is reclaimed for re-use.

The generator, of course, may be applied as a hook-up in a system wherein the filters are omitted, particularly on water storage lines, wherein the Water generally has already been filtered. Also the water purification gas generator may be applied to Water systems where the water is not to be used for drinking purposes, merely to destroy contaminating organic matter. It is also possible to treat large bodies of water by merely using a series of perforated pipes suspended in the water such as in ponds, swimming pools, rivers, harbors and bays as well as storage tanks for drinking or waste waters. In some instances it will be understood it may be desirable merely to decontaminate sewage waters by killing the bacteria therein without oxidation of all of the suspended organic matter content. In such cases the supply of the activated gas will be limited to obtain the result desired, that is for example destruction of the bacteria content without substantial removal of the organic matter.

Thus, as shown in Fig. 2 the supply of activated gas may be applied through any porous member 17 shown in this figure as a perforated pipe lying at the bottom of a large body of Water through which activated gas bubbles are emitted. Such body of water may be as described, in a tank or large, relatively stagnant body of water, but

may also comprise a large body of moving water unconned, such as a riveror stream.

Fig. 3 shows the application of the gas to a line 10 leading to an oil well of conventional construction wherein the line 10 would carry either contaminated water, generally available in the vicinity of the well or drilling muds made up therefrom. It is desirable to use a setup as shown in Fig. l having a gas separating chamber 18, similarly situated upon the water line to separate the gases which are not actually dissolved andy prevent introduction of excessive quantities of gas into the well.

The following examples illustrate the practice of this invention:

Example 1.-A 500 cc. sample of water was taken from the bay at Miami, Florida at a temperature of 65 F. and treated with gas produced by ay generator as described above wherein a catalyst was used consisting of sea water containing an additional content of sodium chloride sufficient to saturate the sea water therewith and to allow some of the sodium chloride to settle as a slurry at the bottom of the catalyst tank to maintain the same continuously saturated. The activated gas was formed by passing oxygen gas from a supply tank of pure compressed oxygen at a rate 11/2 liters per minute. The gas was first heated to a temperature of 150 F. and the generator was maintained at a pressure of 40 lbs. gauge. It was first passed through a tank containing ultra violet lamps radiating light at a wave length of 2486 angstrom units and thence through a second tank containing high voltage electrodes maintained at a volt discharge of 15,000 volts produced by a transformer operated at an input voltage of 110 volts and thence through the sea water catalyst saturated with sodium chloride and finally at the same rate of 11/2 liters per minute through the 500 cc. sample of Miami bay water. The following table shows the results of the tests:

Bacteria Count Color Odor Time, Minutes Before After Before After Before After None.

changed from a yellowish tinge to crystal clarity:

Bacteria Count Color Odor Time, Minutes Before After Before .After Before After Crystal Clear.

None.

ExumpleIlI.-In another sample taken from the same Iriver closely'adjacent to a sewageA waste outlet passin-g into the river, the bacteriall count was 27,00()I per cc'.

and in l0 minutes with a gas flow of 1%` liters perv minute was' reduced to a negligible value, and in l minute the sample became colorless.

Time Bacteria Color Odor Solids Count 0 27,000 Ye11ow Colorlessin None. Present.

lmin.). 110 Colorless 60 11 6 3 3 Reduced.

Example 1V.-AVY swamp containing highly contaminated stagnant water and overgrown during the Warm weather with .growing algae which coated the same as a scum, rand having an a-rea -of about 1/2 Ian acre and a depth -of water `of abou-t 2 feet, was treated with a `gas formed by passing oxygen under heat .and pressure as described in Example I, the catalyst being a saturated solution in water of sodium hypo chlorite, the gas being generated at :a rate of about 10 liters per minute and passed Ithrough an open pipe having a distributing nozzle of porous stone which extended over the side of a barge upon which the gas generating apparatus, ras described in the drawing herewith, was mounted. The pipe extended approximately 11/2 feet below the vbottom of the barge, the barge being moved slowly up and back over the surface of the .pond for 8 hours while generating the `gas which lbubbled through the water rand was continuously dissipated in the air. yIt was found that after this treatment no :algae -grew -on the surface of the swamp, the water being substantially clarified for the entire season Vof approximately 6 months. Moreover, the swamp contained no mosquito larvae or exhibited other evidence of bacterial or insect larval contamination and Ithe Water was substantially odorless yover the period of the ltes-t.

As an alternate procedure this example was repeated 'applying a simultaneous-ly polymerized mixture of oxyigen containing 15% of chlorine gas by volume, by exposing the gas mixture at :a tempera-ture of iF. and pressure of 50 lbs. gauge to ultra violet light ofwave` length of 2500 angstrom units land then exposing to Ia :discharge of 18,000 volts and directly using the Isame without further catalysis. After 8 hours of treatment the swamp was similarly purified.

Example V.-A test was performed upon condenser cooling water Ion a ship wherein sea water was passed at `a rate of 600 lgallons per minute for purposes of condensing steam from a steam power plant operating the ship. Prior to this treatment the cooling water Ilines were contaminated with organic matter, such las algae and organic scums which -coated the surfaces of the piping and "condenser tubes. The gas generator was mounted -as described in the drawing hereinabove to generate and pass halogen activa-ted gas into the system, at a rate `of 10 liters of gas per minute the `gas being removed and bled `off from time to time through a vent in the top `of the condenser. It was found that within 6 hours after yoperation the lines were substantially clean includ-ing the condenser shell and condenser tubing, lar-ge quantities of inorganic lscale was loosened from the walls and removed from the condenser hot well.

Example Vl.-To show the eiect of activated gas upon certain land definite bacteria cultures, several cultures of pure bacteria were `formed in suspensions of each culture in 500 cc. of water. Samples were treated by `bubbling lactivated :gas at a rate of 1.1/2 liters per minute through each sample. `In each case :a 500 cc. sample was used for control purposes which was not treated with the gas. The gas itself was for-med similar to the previous examples using sodium hypochlorite in' saturated solution in sea water :as the catalyst. it will 'be understood that the samples were made up by" im noculating each 500 ec. sample with Ithe pure strain of bacteria, allowing usual incubation time and then treatring. And in the case of the control -no treatment with the activated lgas was applied. The `following ltable shows the results on several bacterium:

Bacteria Treated Group Control Group H. influenzae saline suspension No growth Gwth in 48 ours. D. pneumoniae saline suspension. Do. E. coli Sahne suspension Growth in 24 hours. B. abortus saline suspension do Do. B. abortus broth culture No growth in 24 Do.

, hrs.; some growth in 72 hours under CO1 tension. B. subtilis saline suspension No growth Do. M. tuberculosis saline suspension-.. No growth in 8 Growth in 2-3 wks. observawks.

tion` E. typhosus saline suspension No growth Gilrpwth in 24 ours. Cl. telani saline suspension Growth in 24 hrs Do. Cl. tetani broth culture do Do. M. albicans saline suspension No growth Do.

The treated organisms received ve to eight minute exposure to the gas by bubbling it through the suspension. It is noted lthat in certain instances the bacteria generally of the lspore forming type for example Cl. tetan showed immediate :growth in 24 hours, similar to the control sample.

-Example VIL-To illustrate the superior effect of iodine for :treatment of Ithe spore forming type of bactenium Cl. tetani las shown in the previous example, was treated both in saline and broth culture in the same manner as in Example VI with the difference that potassium 'triiodide was used as Ilthe catalyst and .in this instance no growth was obtained of the bacterium in 24 hours either in saline suspension or broth culture whereas the cont-rol of course, showed the same results as in the previous example.

Example VIM-The controls of Example VI after growth as indicated in Example VI, was treated by exposing the control in a subsequent test for a period of 5 to 8 minutes, the same gas flowing at 11/2 liters per minute through each sample in each case, with the exception of Cl. tetan, was destroyed by the brief treatment with gas. The Cl. tetan was treated as described in Example VII with an iodine halogenated gas as described in Example VII and the control likewise showed no evidence of bacteria.

Example IX.-Polymerized oxygen gas containing at least 60% of polymeric oxygen directly as obtained by ultra violet light exposure Iand high voltage treatment at high pressure and temperatures, as described hereinabove, is passed by bubbling through a liter of water for a period of forty minutes. The solution is then placed in gas tight container and subsequently applied as a laundry bleach. It was found to rapidly Whiten cotton goods placed in the solution.

Example X.-A bleach solution was made up as in Example IX with the modification that the gas prior to :aeration of the water was first passed through a catalyst solution comprising la concentrated solution of calcium hypoachlorite in sea water. This gas after aeration of water to saturation as described in Example IX was found to be an extremely active bleach solution for raw washed cotton dipped therein.

Example XI.-The gas of Example X was injected into Water under pressure of 50 lbs. per square inch and sealed in a container under this pressure and was found to be a highly active bleaching solution similar to Examples IX and X.

' Example XII.-The solution of Example XI was applied yasan agricultural spray to a tree under attack by fungus. It was found'that the solution after drying had killedthe fungus.l

Gli

Example XUL-The solution of Example IX was used for washing raw citrus fruit prior to packaging, It was found that the fruit was resistant to destruction by mold as compared to unwashed fruit.

Example XIV.-A suspension of adequately beaten paper pulp is bleached by passing halogen :activated gas through the pulp for one hour While Iagitating the pulp to obtain homogeneous oxidation thereof.

According to another modification of the present invention the highly polymerized oxygen gas directly as obtained or with a further halogen content obtained by adding halogen to the oxygen prior to polymerizing or by passing polymerized gas through the catalyst solution, is dissolved in the water to a point of saturation to impart thereto a maximum quantity of the gas. For this purpose gas is bubbled through 'a column of water until the water absorbs as much as will dissolve, a quantity generally exceeding l cc. of gas per liter of water; and preferably the gas is passed through the water under pressure or may be injected under pressure into a container partially filled with water similar to typical carbonation of water. The excessive quantity of polymerized oxygen in the water acts as an oxidizing agent where the fluid is applied for oxidizing purposes, such as, as a bleach solution for laundry, paper pulp, etc. or .as an agricultural spray for the destruction of fungus, bacteria or insects, in view of the extremely active biocidal properties of the gas. Of course the bleaching may 'also be effected by first suspending the material to be bleached such as cloth, laundry, paper pulp, etc., in the water and then passing the gas therethrough, or both oxidizing gas and material to be bleached or oxidized, disinfected, etc., may be simultaneously added to the water wit-l1 the gas at rates adjusted to the degree of contact required.

Various other modifications of the present invention will occur to those skilled in the art. For example the activated gas hereof may be applied to waters to be used in ice making or waters which contain other salts such as brines used in deep freezing. Similarly, other methods of contacting the water with the activated gas to effect purification thereof may be applied, for example, the gas and the water may be simultaneously sprayed to effect contact. The water may be used in various places where a highly purified water is desired. For

1:, example Waters that would normally be distilled for use in medications or as carrier therefor, may be treated by the present method. Similarly, where waters are to be carbonated in soft drinks such water may be treated with the present gas prio-r to carbonation or the gas may be mixed with the carbon dioxide zand the water carbonated and purified simultaneously. Similarly, the gas generating apparatus may be mounted 'as part of a water treating assembly such as with `a typical drinking fountain, particularly where the Water is to be refrigerated.

It is laccordingly intended that the disclosure and description hereof be regarded 'as exemplary and not limiting except as defined in the claims appended hereto.

I claim:

1. The method of purifying Water comprising passing i-nto the water a gas comprising a halogen activated polymeric oxygen, said polymeric oxygen consisting essentially of gas which has been polymerized by treating the same under conditions to convert a substantial proportion of the oxygen to ozone and higher polymerized forms of oxygen, and being halogen activated by contact of the polymeric oxygen gas with elemental halogen and salts thereof.

2. The method of purifying water comprising passing into the water a gas comprising polymeric oxygen which has been activated by incorporating therein a minor content of halogen, said polymeric oxygen consisting essentially of oxygen gas which has been polymerized by treating the same under conditions to convert a substantial proportion of the oxygen to ozone and higher polymerized forms of oxygen.

3. The method of purifying water comprising passing into the Water a gas comprising polymeric oxygen which has been activated by passingthe same through a catalyst comprising a concentrated aqueous solution of halogen material selected from the group consisting of elemental halogen and water-soluble salts thereof, said polymeric oxygen consisting essentially of oxygen gas which has been polymerized by treating the same under conditions to convert a substantial proportion of the oxygen to -ozone and higher polymerized forms of oxygen.

y4. The method of purifying water comprising passing into the water oxygen gas which has been polymerized and further activated by passing the same through sea water which has been saturated with a halogen material selected from the group consisting of elemental halogen and Water-soluble salts thereof said polymeric oxygen consisting lessentially of oxygen gas which has been polymer'ized by treating the same under conditions to convert a substantial proportion of the oxygen to ozone and higher polymerized forms of oxygen.

v5. The method of destroying organic matter and bacteria in contaminated water comprising passingl into the Water a gaseous oxidizing agent comprising halogen activated polymeric oxygen for a period of time sufficient to at lleast partially oxidize the organic matter therein, said polymeric oxygen consisting essentially of gas which has been polymerized by treating the same under conditions to convert a substantial proportion of the oxygen to ozone and higher polymerized forms of oxygen, and being halogen activated by contact of the polymeric oxygen gas with elemental halogen and salts thereof.

'6. The method of decontaminating drinking Water comprising passing into the Water a halogen activated polymeric oxygen gas for a period of time suicient to destroy bacteria, said polymeric oxygen consisting essentially of gas which has been polymerized by treating the same under conditions to convert a substantial proportion of the oxygen to ozone and higher pclymerized forms of oxygen, and being halogen activated by contact of the polymeric oxygen gas with elemental halogen and salts thereof.

7. The method of decontaminating waste water comprising bubbling through the Water a halogen activated polymeric oxygen gas, said polymeric oxygen consisting essentially of gas which has been polymerized by treating the same under conditions to convert a substantial proportion of the oxygen to ozone and higher polymerized forms of oxygen, and being halogen activated by contact of the polymeric oxygen gas with elemental halogenand salts thereof.

8. The method of decontaminating Water storage and piping systems containing Water comprising applying to the water contained therein a gaseous oxidizing agent comprising a halogen activated polymeric oxygen gas, said polymeric oxygen consisting essentially of gas which has been polyinerized by treating the same under conditions to convert a substantial proportion of the oxygen to ozone and higher polymerized forms of oxygen, and being halogen activated by contact of the polymeric oxygen gas with elemental halogen and salts thereof.

9. A method of purifying water comprising `first filtering the water to remove suspended insoluble contaminants and then passing therein a halogen activated polymeric oxygen gas in quantities suflicient to destroy the bacteria and oxidize at least a part of the organic matter, said polymeric oxygen consisting essentially of gas which has been polymerized by treating the same under conditions to convert a substantial proportion of the oxygen to ozone and higher polymerized forms of oxygen, and being halogen activated by contact of the polymeric oxygen gas with elemental halogen and'salts thereof.

1Q. ln the treatment of sewage sludge .highly contaminated with bacteria the step of passing into said liquid suspension of sewage a halogen activated polymeric oxygen gas, said polymeric oxygen 'consisting essentially of gas which has been 'polymer-ized by treatingfthe santeunder conditions toyconv'ert :a substantial proportion 'of the oxygen to ozone .and higher polymerized 'forms-fof` oxygen, and being halogen activated bycontac't of the polymeric oxygen gas"wi`th elemental halogen 'and' Vsaltsing the same under conditions to convert a substantialV proportion of the oxygen to ozone and higher polymeri-zed forms of oxygen, and being halogen activated by contact of the polymeric oxygen gas with elemental halogen and salts thereof.

l2. The method of decontaminating water comprising passing into the Water a gas formed by polymerizing a mixture of halogen and oxygen, said polymeric oxygen consisting essentially of gas which has been polymer-ized by treating the same under conditions to convert a substantial proportion of the oxygen to ozone and higher polymerized forms of oxygen, and being halogen activated by contact of the polymeric oxygen gas with elemental halogen and salts thereof.

13. The method of decontaminating water comprising passing into the water a gas formed by passing polymerized oxygen and `halogen simultaneously through an aqueous salt solution, said polymeric oxygen consisting essentially of oxygen gas which has been polymerined by treating the same under conditions to convert a submential proportion of the oxygen to ozone and higher polymerized forms of oxygen. Y

1,4. The method :as defined in claim l wherein 'the halogen is iluorine. l

l155. The method :as defi-ned in claim l wherein the hnlogen .is bromine` Y 1.6. The method as dened inclaim 1 wherein the halogen is chlorine. v f

Y17. The method as defined in claim 1 wherein the halogen is iodine.

118. The method as defined in claim l wherein th halogen is a mixture of halogens. Y

I19.. The-method of purifying Water comprising lirradiating oxygen gas with ultra violet iight and then subjecting the irradiated oxygen to a high voltage discharge exceeding 5,000 volts while maintaining the gas at raised temperatures and pressures and then passing said gas through the water to be purified.

20. The method of purifying an aqueous liquid contaminated with micro-organisms comprising passing in-to said liquid a gas containing'oxygen, ozone, and halogen.

21. In the decolorization of Water and organic materials suspended therein, the step of passing into said Water ahalogen activated polymeric oxygen gas `suiiicient to reduce the color thereof, said polymeric oxygen consisting essentially of gas which has been polymerized by treating the same under conditions to convert a substantial proportion of the oxygen to ozone and higher polymerized forms of oxygen, and being halogen activated by contact lof the polymeric oxygen 'gas with 'e'lemental halogen and salts thereof.

' 22. In the washing of fresh fruits and vegetables 'for storage and transit, the step of treating the water to destroy bacteria therein by passing into the water a halogen activated polymeric oxygen, said polymeric oxygen consisting` essentially of gas which has been polymerized by treating the same under conditions to convert a substantial proportion of the Yoxygen to ozone and higher polymerized forms of oxygen, and being halogen activated by contact of the polymeric oxygen gas with elemental halogen and salts thereof. n

23. The method of purifying water, comprising passing oxygen gas containing ozone in substantial concentration therein through a concentrated aqueous 'solution of a halogen material and then passing into the water to be puried the gas thus formed.

References Cited in the le of this patent UNITED STATES PATENTS Leeds May 22, 1888 Dittrich Apr. 14, 1891 Lovejoy Aug. 28, 1906 Woolf July 7, 1908 Weiner Oct. 24, 1911 Kriegsheim Sept. 12, 1916 MacGregor et al June 20, 1922 Wait My 9, 1933 OTHER REFERENCES Vosmaer: Ozone 1916, D. Van Nostrand Co., N. Y. pages 3, 12, 13, 25, 26, 72 and 30 relied upon. 

1. THE METHOD OF PURIFYING WATER COMPRISING PASSING INTO THE WATER A GAS COMPRISING A HALOGEN ACTIVATED POLYMERIC OXYGEN, SAID POLYMERIC OXYGEN CONSISTING ESSENTIALLY OF GAS WHICH HAS BEEN POLYMERIZED BY TREATING THE SAME UNDER CONDITIONS TO CONVERT A SUBSTANTIAL PROPORTION OF THE OXYGEN TO OZONE AND HIGHER POLYMERIZED FORMS OF OXYGEN, AND BEING HALOGEN ACTIVATED BY CONTACT OF THE POLYMERIC OXYGEN GAS WITH ELEMENTAL HALOGEN AND SALTS THEREOF. 